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Improving the predictive quality of time?dependent density functional theory calculations of the X?ray emission spectroscopy of organic molecules

Fouda, Adam A. E.; Besley, Nicholas A.

Improving the predictive quality of time?dependent density functional theory calculations of the X?ray emission spectroscopy of organic molecules Thumbnail


Authors

Adam A. E. Fouda

Nicholas A. Besley



Abstract

The simulation of x-ray emission spectra of organic molecules using time-dependent density functional theory (TDDFT) is explored. TDDFT calculations using standard hybrid exchange-correlation functionals in conjunction with large basis sets can predict accurate X-ray emission spectra provided an energy shift is applied to align the spectra with experiment. The relaxation of the orbitals in the intermediate state is an important factor, and neglect of this relaxation leads to considerably poorer predicted spectra. A short-range corrected functional is found to give emission energies that required a relatively small energy shift to align with experiment. However, increasing the amount of Hartree-Fock exchange in this functional to remove the need for any energy shift led to a deterioration in the quality of the calculated spectral pro?le. To predict accurate spectra without reference to experimental measurements, we use the CAM-B3LYP functional with the energy scale determined with reference to a ?self-consistent ?eld (SCF) calculation for the highest energy emission transition.

Citation

Fouda, A. A. E., & Besley, N. A. (2020). Improving the predictive quality of time?dependent density functional theory calculations of the X?ray emission spectroscopy of organic molecules. Journal of Computational Chemistry, 41(11), 1081-1090. https://doi.org/10.1002/jcc.26153

Journal Article Type Article
Acceptance Date Jan 8, 2020
Online Publication Date Jan 22, 2020
Publication Date Apr 30, 2020
Deposit Date Jan 23, 2020
Publicly Available Date Mar 29, 2024
Journal Journal of Computational Chemistry
Print ISSN 0192-8651
Electronic ISSN 1096-987X
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 41
Issue 11
Pages 1081-1090
DOI https://doi.org/10.1002/jcc.26153
Keywords General Chemistry; Computational Mathematics
Public URL https://nottingham-repository.worktribe.com/output/3787403
Publisher URL https://onlinelibrary.wiley.com/doi/full/10.1002/jcc.26153
Additional Information Received: 2019-10-15; Accepted: 2020-01-08; Published: 2020-01-22

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